Dry blend fracturing fluid additives

ABSTRACT

A method and composition for crosslinking a polymer based fluid includes providing a dry blend of crosslinker and delay agent. The crosslinker and delay agent are mixed and granulated in a dry form prior to addition to the polymer fluid.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates generally to additives for fracturingfluids. More specifically, the invention is a dry, granulated blendcomprising a crosslinker and a delay agent.

2. Description of the Prior Art

In the recovery of hydrocarbons from subterranean formations it iscommon practice, particularly in formations of low permeability, tofracture the hydrocarbon-bearing formation, providing flow channels.These flow channels allow the oil or gas to reach the wellbore so thatthe oil or gas may be pumped from the well.

Water-based hydraulic fracturing fluids usually contain a hydratablepolymer that acts to thicken the fracturing fluid and may be furtherthickened by chemically crosslinking Such a polymer typically ispresented in a powder form, or in a slurried form in a hydrocarbon suchas diesel, and is hydrated upon the surface of the ground, for examplein a batch mix liquid operation in large mixing tanks for a significantperiod of time, and then mixed with other liquid additives of varioustypes using large expensive equipment. After hydration, the polymer istypically crosslinked to further thicken the fluid and improve itsviscosity at elevated temperatures often encountered in the fracture, soit can carry proppant into the fracture once it is pumped into awellbore below the ground surface. Natural polymers includepolysaccharides, such as guar and derivatives of guar such ashydroxypropyl guar (HPG), carboxymethylhydroxypropyl guar (CMHPG),carboxymethyl guar (CMG), or hydrophobically modified guar. Borate,zirconium and titanium containing crosslinking agents typically areused. Both borate and organometallic crosslinking agents offeradvantages depending upon the fluid performance and cost requirements ofthe particular fracturing treatment.

Numerous chemical additives such as antifoaming agents, acids or bases,or other chemicals may be added to provide appropriate properties to thefluid after it is hydrated. Other additives commonly included infracturing fluids include viscosity stabilizers, activators forcrosslinking, shear recovery agents, hydration enabling agents and claystabilizers. Generally, a viscosity stabilizer is an additive used toretard the polymer degradation from the effects of temperature, shearand iron exposure. A clay stabilizer prevents the swelling or migrationof the clays in the formation.

Polymer based hydraulic fracturing fluids are well known in the oilfieldservices industry. These fluids are routinely used to treat and fracturesubterranean formations to increase production from these formations.Typically, the fluid is prepared or mixed at the surface by combining anumber of liquid additive streams with a hydrated polymer fluid. Thefluid is then pumped downhole with sufficient pressure to accomplish thetreatment. In certain cases, the fluid may be used to transport proppantor other additives to the formation. The viscosity of the fluid is oftenan important consideration in the job design. The fluid must havesufficient viscosity to transport any included solids, such as proppant;however, it cannot be so viscous that it cannot be economically pumpeddownhole.

Crosslinkers are commonly used to increase the viscosity of polymerbased fracturing fluids. The crosslinker chemically connects or bondsthe polymer chains in the fluid, thereby increasing viscosity. Wellknown crosslinkers of polymer fluids include boron-, zirconium- andtitanium-containing compounds. In many cases, the use of a crosslinkeralone causes a very rapid increase in the viscosity of the fluid and maypresent significant problems in terms of handling and pumping theviscosified fluid (i.e., the amount of horsepower required to pump thehighly viscous fluid downhole is greater than that typically provided atthe jobsite). To alleviate this problem, the crosslinking of the polymercan be delayed for a predetermined time. In this way, the fluid does notreach its full viscosity until it is downhole. Delay agents are commonlycombined with the crosslinker prior to mixing the crosslinker with thepolymer fluid.

Delay of the crosslinking mechanism of the polymer can be achieved usingdifferent means. One method is to physically trap or sequester thecrosslinker inside a capsule that will dissolve with time under certainconditions of temperature, pH, pressure etc. Alternatively, thecrosslinker may be bound to or reacted with another chemical (i.e., adelay agent). The release from this chemical delay agent will also be afunction of time, temperature and relative concentrations of thecrosslinker and delay agent. The delay in the crosslinking reaction isdue to a ligand exchange between the crosslinker, the delay agent andthe polymer. In simplified terms, the delay is determined by the timerequired by the crosslinker to “escape” from the delay agent andcrosslink the polymer.

Although the fluid additives, including crosslinker and delay agents,are typically provided in liquid form, it is known that certain of theseadditives or in some cases the additives and polymer may be provided ina dry form. For instance, U.S. Pat. No. 5,372,732 (Harris), teaches adry, granulated, delayed crosslinking agent. A borate crosslinker iscombined with a liquid polysaccharide solution to produce a fluidcontaining highly crosslinker polymer. This solution is then dried andgranulated and may then be added to a polymer fluid.

Another example of the use of a dry blend of polymer and additives isdescribed in U.S. Pat. No. 5,981,446 (Qiu). A dry blended particulatecomposition which includes the polymer as well as a number of otheradditives is prepared and added to water to produce a fracturing fluid.The specific composition of the fluid must be predetermined andgenerally cannot be changed at the wellsite. This loss of flexibilitycan present signficant problems in terms of job completion. Decreasedflexibility can also be a signficant concern during the design of thejob. For example, in a typical fracturing job, initiation of thefracture is accomplished using a linear (non-crosslinked) fluid thatdoes not contain proppant. Once the fracture is formed, the fluid iscrosslinked and proppant is added. Clearly, two different blends wouldbe needed in this case, one containing a crosslinker, the other one notcontaining the crosslinker.

SUMMARY OF THE INVENTION

The present invention is directed to a dry, granulated blend orcomposition for thickening or crosslinking polymer-based fracturingfluids. The blend is composed of a crosslinker and a delay agent. Theinvention also describes a method of adding this granulated blend in adry form to a polymer based fracturing fluid typically upstream of theproppant. The number of extra additive streams is reduced as the blendcombines into a single additive two or more products that were typicallyprovided separately. This decreases the complexity of preparing ormixing the fluid, thereby decreasing the cost and time required toproduce the fluid and perform a fracturing job or other formationtreatment. In addition, the concentration of the crosslinker and delayagent in the blend are often tied to the concentration of the gellingagent. Therefore, the quality control of the job is better because thetwo critical additives are added at a fixed ratio (the blending is doneahead of the job in a controlled environment as opposed to blending atthe location of the fracturing operation).

The granulated blend is prepared by providing a dry crosslinker and adry delay agent. The crosslinker and delay agent are typically blendedor mixed thoroughly in a dry form to produce a blended crosslinker/delayagent compound. The compound may then be formed into granules. Dependingon the nature of the components (i.e., the crosslinker and the delayagent) it may be necessary to include a binder to aid in the formationand stability of the granules. The relative proportions of crosslinkerand delay agent as well as the granule size may be adjusted to vary tolength of delay, as needed. The dry, blended compound is useful in bothbatch mixed fluids and fluids that are “mixed on the fly.” At no pointduring the preparation of this dry blend, are the individual componentscombined or provided in a liquid form. Similarly, the dry blend is notdissolved or otherwise reduced to a liquid form prior to being shaped orformed into granules.

This dry, granulated compound may be more easily stored and transportedto the wellsite. In addition, preparation of the fracturing fluid issimplified, as the dry blend provides two additives in a single form,thereby reducing the number of additive streams into the fluid. Furtherthe number of operations on location is reduced due to the reducednumber of streams. A dry compound is not subject to freezing, therebyfacilitating use in colder climates. In addition, the concentration ofthe components in the dry blend will not change due to evaporation ofsolvent. This is particularly beneficial in warmer climates. Yet anotheradvantage of the dry blend is a reduction in the volume and weight ofthe product, as compared to a liquid additive. Further, crosslinkeractivity, particularly zirconium and titanium crosslinkers, has beenshown to decrease with time in solution. The dry blend of the presentinvention reduces the time that the crosslinker is in solution prior tobeing combined with the polymer, thereby maintaining a higher and moreconsistent level of activity.

Depending on the specific application in which the compound will beused, it may be desirable to include any number of additional additivesin the compound. As previously mentioned, a binder may be included toaid in the manufacturing of the dry compound. In addition, the compoundsmay also include a viscosity stabilizer, particularly a high temperaturestabilizer, an activator or a clay stabilizer.

Using similar principles as those described above for a drycrosslinker/delay agent compound, other fluid additives may be combinedin dry form to produce a single dry and/or granulated additive. Forinstance, the crosslinker may be combined with an activator, a viscositystabilizer, a shear recovery agent or a hydration enabling agent,instead of the delay agent. Similarly, the delay agent may be combinedwith any number of suitable additives, including activators,stabilizers, shear recovery agents, hydration enabling agents and thelike.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graph showing delay time as a function of the concentrationof the delay agent.

FIG. 2 is a graph showing viscosity over time for a polymer fluid.

FIG. 3 is a graph showing the effect of granule size on delay time.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The present invention is a combined crosslinker and delay agent providedin a dry form. Preferably, the crosslinker/delay agent is provided in agranulated form. As opposed to dry additives, particularly crosslinkersand delay agents, which have been developed in the past, the presentinvention does not require that the individual components (i.e., thecrosslinker and the delay agent) be mixed or complexed in liquid formbefore being dried. The crosslinker and delay agent may both be combinedin dry form to produce a dry compound.

Crosslinkers useful in the present invention are those that are capableof crosslinking a polymer. In a preferred embodiment, the crosslinkercontains boron. More preferably, the crosslinker is boric acid, borax,alkaline earth metal borates, alkali earth metal borates or mixturesthereof. Alternatively, the crosslinker may be a zirconium or titaniumcompound, or a combination or mixture of any of the above mentionedcompounds.

Similarly, any number of delay agents may be used in the presentinvention. Examples of suitable delay agents include, but are notlimited to, polyols, sodium gluconate, sorbitol, a carbonate salt or acombination of the above.

In addition to the crosslinker and delay agent, any suitable number ofadditional additives may be included in the dry blend material. In apreferred embodiment, a binder may be included to physically stabilizethe dry blend and aid in granulation. Other additives include, but arenot limited to, a crosslinker activator, a high temperature stabilizer,a breaker, a shear recovery agent and a clay stabilizer. In a preferredembodiment, the stabilizer may be an oxygen scavenger, a polyol or acarbonate salt. The clay stabilizer may be any suitable composition, butis preferably a salt such as potassium chloride. In a preferredembodiment, the breaker may be composed of an encapsulated ornon-encapsulated oxidizer.

The specific delay time provided by the product of the present inventionmay be adjusted or modified through a number of parameters. The specifictype and relative amount of crosslinker and delay agent are the twoprimary factors. However, granule size, fluid pH, temperature, therelative size of the particles being blended and the presence of anexternal delay agent, crosslinker or activator all may be used to effectthe delay time provided by the granulated product.

The method of the present invention comprises providing a polymer fluid,wherein the fluid may be either fully or partially hydrated. A dry fluidadditive is then mixed with the polymer fluid. The fluid additivecomprises a granulated compound that includes a crosslinker and a delayagent.

In a first embodiment, the method of the present invention comprisesmixing the polymer fluid and the additive in a single tank (i.e., batchmixing). The polymer is combined with a liquid and allowed to at leastpartially hydrate. The additive is then combined with the polymer fluid.Once the fluid and the additive are combined, the fluid may then bepumped downhole. In a second embodiment, the method comprises mixing thecomponents “on the fly.” In other words, the components are mixed as thefluid pumped downhole. It is important to note that thecrosslinker/delay agent additive is provided in a dry form prior tocombination or addition to the polymer fluid.

In an alternative embodiment, the dry crosslinker/delay agent additivemay be added to or combined with a dry polymer. The combined additiveand polymer may then be mixed with a suitable liquid stream to produce apolymer based fluid.

EXAMPLES

The following examples illustrate certain embodiments of the presentinvention.

FIG. 1 shows the delay obtained as a function of the concentration ofdelaying agent in the dry blend. The samples were prepared with apolymer fluid having a loading of 35 pounds per 1000 gallons (ppt). Thepolymer was fully hydrated in this example; however, in certainapplications, it may be possible to add the crosslinker/delay agentbefore the polymer is fully hydrated. The polymer used in theexperiments was guar. It should be understood that while guar was usedin the example, any suitable polymer or gelling agent may be used.Preferably, the polymer is guar or derivatized guar. Preferredderivatized guars include hydroxypropyl guar, carboxymethylhydroxypropyl guar, carboxymethyl guar or any combination of these. Thepolymer fluid was allowed to hydrate for approximately 30 minutes priorto crosslinking The dry blend of crosslinker and delay agent was addedto the fluid while in a blender at 2000 rpm. The crosslinker was presentin an amount of 1.5 pounds per thousand gallons (ppt) of fluid. Theamount of delay agent varied from 0 ppt to approximately 8.5 ppt.Following addition of the crosslinker/delay agent, a caustic solution(0.45 gallons per thousand gallons (gpt) of 28% solution of causticsoda) was added and the fluid was further mixed for 10 seconds. Theinitial lip time and the final lip time were recorded for each sample.The initial lip time indicates the time required for a polymer fluid todevelop an initial viscosity. The final lip time indicates the timerequired for the polymer to reach full viscosity. The crosslinker usedwas boric acid and the delay agent was sodium gluconate. Both were addedsimultaneously in the form of a powder. These results show that thecrosslinker and the delay agent may be added in dry form, without priorreaction or dissolution, to crosslink a polymer fluid.

The following procedure was used in determing the lip times: theprepared fluid is poured from a container until a tongue approximatelythree-quarters of an inch is formed and can be retracted back into thecontainer. This is the intial lip time. The final lip time is the timeat which a two inch tongue can be poured and retracted.

In addition to use with guar-based fluids, the crosslinker/delay agentof the present invention was also tested with a CMHPG-based fluid. A 35ppt CMHPG fluid was prepared and hydrated. The pH of the fluid wasadjusted to approximately 9.46 with a 5% caustic soda solution. A 200 mLsample of the CMHPG fluid was then crosslinked with a dry blendcontaining sodium zirconium lactate and sodium gluconate in a molecularratio of 40:1. The dry blend was mixed into the fluid for approximately10 seconds. The final crosslinking time was approximately 45 seconds,which indicates that crosslinking was delayed by the dry blend. Forpurposes of comparison, a typical CMHPG polymer fluid under the sameconditions without a delay agent would have a crosslinking time of lessthan 10 seconds.

FIG. 2 shows the stability of a fluid prepared using a dry, granulatedcrosslinker/delay agent. A base fluid comprising 35 ppt of dry guar washydrated in a blender for approximately 30 minutes. The fluid was thencrosslinked by adding a granulated blend at 4.7 ppt (which correspondsto 1.5 ppt boric acid and 3.0 ppt sodium gluconate and further includingbinder and anti-caking agents in an amount of approximately 2 wt %. Theactivator was a liquid solution of 28% caustic soda used at 0.45 gpt.The viscosity of the crosslinked fluid was then measured and recordedover time at 200° F. in a Fann 50 rheometer. As can be seen, the fluidremained stable and maintained a suitable viscosity at temperature forapproximately 2 hours, at which point no further measurements weretaken.

FIG. 3 shows the difference in delay time when the crosslinker/delayagent is added in a crushed or powdered form and granulated form. A basepolymer fluid was prepared having a polymer loading of 35 ppt. The fluidwas hydrated in a blender for approximately 30 minutes. Followinghydration, the fluid was crosslinked with 0.45 gpt of a solution of 28%caustic soda and a crosslinker/delay agent combination having 1.5 pptboric acid and 3.75 ppt sodium gluconate. The crosslinker/delay agentwas added in a dry, crushed form and a first granular form (mesh size10/20 (i.e., average particle diameter of 1.26 mm)) and a secondgranular form (mesh size 4/10 (i.e., average particle diameter of 3.38mm)). The results show that the larger the particle diameter, the longercrosslinking is delayed, as the delay is a function of the surface areaof the granule subject to dissolution. In addition, the results showthat the granulated dry blend additive does crosslink the polymer fluidand does provide a suitable delay.

In addition to combining a crosslinker and delay agent in a dry blend,as previously described, the present invention may include any number ofadditional dry components blended together to form a single, dryadditive. For instance, magnesium oxide, an activator, and sodiumgluconate, a delay agent, may be combined in dry form to produce a dryblend for delaying the crosslinking of a polymer fluid. To illustratethis, a 35 ppt guar solution was prepared and hydrated. An equivalent of2 ppt of boric acid and 5 ppt of magnesium oxide, in the form of 0.42grams of a dry blend containing magnesium oxide and boric acid in a2.5:1 ratio, was added to 500 mL of the hydrated guar solution and theresultant fluid mixed for approximately 10 seconds. Following this, wasadded and the fluid. The first lip appeared at 1 minute and the finalcrosslink time was approximately 2 minutes. A similar experiment wasthen conducted with a similar guar-based fluid. A 35 ppt guar solutionwas prepared and hydrated. An equivalent of 2 ppt of boric acid was thenadded to 500 mL of the hydrated guar solution and the resultant fluidwas mixed for 30 seconds. A dry blend of MgO and sodium gluconate, in a1:1 ratio, was then added in place of the MgO/boric acid blend. Thefinal crosslink time was approximately 4 minutes.

1-22. (canceled)
 23. A polymer fluid with delayed crosslinking,comprising: (a) a crosslinker; and (b) a delay agent selected from thegroup consisting of polyols, sodium gluconate, sorbitol, carbonatesalts, and combinations thereof; wherein the crosslinker and the delayagent are a dry, granulated compound.
 24. The fluid of claim 23, whereinsaid crosslinker contains boron.
 25. The fluid of claim 23, wherein saidcrosslinker contains zirconium.
 26. The fluid of claim 23, wherein saidcrosslinker contains titanium.
 27. The fluid of claim 23, wherein saidcrosslinker comprises at least two or more of the following: a boroncontaining compound, a titanium containing compound and a zirconiumcontaining compound.
 28. The fluid of claim 24, wherein said crosslinkeris selected from the group consisting of: boric acid, borax, alkalineearth metal borates, alkali earth metal borates or mixtures thereof. 29.The fluid of claim 23, wherein said delay agent is selected from thegroup consisting of: sodium gluconate, sorbitol or a combinationthereof.
 30. The fluid of claim 23, wherein the dry, granulated compoundcontains no crosslinkable polymer.
 31. The fluid of claim 23, furthercomprising a viscosity stabilizer.
 32. The fluid of claim 23, furthercomprising a dry polysaccharide polymer.
 33. The fluid of claim 23,further comprising an activator for the crosslinker.
 34. A method offorming a fluid comprising a fluid additive having utility for additionto a polymer fluid for delayed crosslinking, comprising: a) providing afluid comprising a polymer; b) providing a fluid additive comprising: i)a dry crosslinker; and ii) a dry component selected from the groupconsisting of a delay agent and a crosslinker activator; wherein the drycrosslinker and the dry component are single compound granules.
 35. Themethod of claim 34, wherein said first dry component is a crosslinkeractivator.
 36. A method for delayed crosslinking a polymeric fracturingfluid comprising the steps of: a) providing a fluid comprising apolymer; b) providing a fluid additive comprising: i) a crosslinker; andii) a delay agent; wherein the crosslinker and the delay agent are adry, granulated compound; and c) mixing the fluid additive and thefluid.
 37. The method of claim 36, wherein the polymer is guar.
 38. Themethod of claim 37, wherein the polymer is a derivatized guar.
 39. Themethod of claim 37, wherein said derivatized guar is selected from thegroup consisting of: hydroxypropyl guar, carboxymethylhydroxypropylguar, carboxymethyl guar and combinations thereof.
 40. The method ofclaim 36, wherein said fluid additive is batch mixed with said fluid.41. The method of claim 36, wherein said fluid additive and said fluidare mixed on the fly.
 42. The method of claim 36, wherein said fluidadditive provides a crosslinker delay from about 30 seconds to about 15minutes.
 43. The method of claim 36, wherein the dry component is freeof the polymer.
 44. The method of claim 36, wherein the fluid furthercomprises a dry polysaccharide polymer.